Relationship between the activity for photocatalytic H_(2)O overall splitting(HOS)and the electron occupancy on d orbits of the active component in photocatalysts shows volcanic diagram,and specially the d^(10)electro...Relationship between the activity for photocatalytic H_(2)O overall splitting(HOS)and the electron occupancy on d orbits of the active component in photocatalysts shows volcanic diagram,and specially the d^(10)electronic configuration in valley bottom exhibits inert activity,which seriously fetters the development of catalytic materials with great potentials.Herein,In d^(10)electronic configuration of In_(2)O_(3)was activated by phosphorus atoms replacing its lattice oxygen to regulate the collocation of the ascended In 5p-band(Inɛ5p)and descended O 2p-band(Oɛ2p)centers as efficient active sites for chemisorption to*OH and*H during forward HOS,respectively,along with a declined In 4d-band center(Inɛ4d)to inhibit its backward reaction.A stable STH efficiency of 2.23%under AM 1.5 G irradiation at 65°C has been obtained over the activated d^(10)electronic configuration with a lowered activation energy for H_(2)evolution,verified by femtosecond transient absorption spectroscopy,in situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations of dynamics.These findings devote to activating d^(10)electronic configuration for resolving the reaction energy barrier and dynamical bottleneck of forward HOS,which expands the exploration of high-efficiency catalytic materials.展开更多
The conversion rules under which an algebraic expression can be obtained from a corresponding photoionizationGoldstone diagram have been given systematically in the present work.The electronic correlations in thephoto...The conversion rules under which an algebraic expression can be obtained from a corresponding photoionizationGoldstone diagram have been given systematically in the present work.The electronic correlations in thephotoionization processes then could be studied diagrammatically.The application to atomic scandium shows that thepresent theoretical scheme can give reasonable photoionization cross sections,which agree well with the experimentalresults.展开更多
文摘Relationship between the activity for photocatalytic H_(2)O overall splitting(HOS)and the electron occupancy on d orbits of the active component in photocatalysts shows volcanic diagram,and specially the d^(10)electronic configuration in valley bottom exhibits inert activity,which seriously fetters the development of catalytic materials with great potentials.Herein,In d^(10)electronic configuration of In_(2)O_(3)was activated by phosphorus atoms replacing its lattice oxygen to regulate the collocation of the ascended In 5p-band(Inɛ5p)and descended O 2p-band(Oɛ2p)centers as efficient active sites for chemisorption to*OH and*H during forward HOS,respectively,along with a declined In 4d-band center(Inɛ4d)to inhibit its backward reaction.A stable STH efficiency of 2.23%under AM 1.5 G irradiation at 65°C has been obtained over the activated d^(10)electronic configuration with a lowered activation energy for H_(2)evolution,verified by femtosecond transient absorption spectroscopy,in situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations of dynamics.These findings devote to activating d^(10)electronic configuration for resolving the reaction energy barrier and dynamical bottleneck of forward HOS,which expands the exploration of high-efficiency catalytic materials.
基金The present study was part of The University Science & Technology Planning Program of Shandong Province under Grant No. J10LB60 (self-financing)partly supported by the Natural Science Foundation of Shandong Province under Grant No. ZR2011AM010 and 2009 Technology Innovation Fund (09L026) of Ludong University
文摘The conversion rules under which an algebraic expression can be obtained from a corresponding photoionizationGoldstone diagram have been given systematically in the present work.The electronic correlations in thephotoionization processes then could be studied diagrammatically.The application to atomic scandium shows that thepresent theoretical scheme can give reasonable photoionization cross sections,which agree well with the experimentalresults.
